(4S)-(-)-2,4-dibenzyl-2-oxazoline | 77937-53-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (4S)-(-)-2,4-dibenzyl-2-oxazoline
• 英文别名: (S)-2,4-dibenzyl-2-oxazoline；(s)-2,4-Dibenzyloxazoline；(4S)-2,4-dibenzyl-4,5-dihydro-1,3-oxazole
• CAS: 77937-53-2
• 化学式: C₁₇H₁₇NO
• 分子量: 251.328
• InChiKey: CXJLMGDRFVTPFA-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4S)-(-)-2,4-dibenzyl-2-oxazoline 、 碘甲烷 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以59%的产率得到(4S)-4-benzyl-2-(1-phenylethyl)-4,5-dihydro-1,3-oxazole
  参考文献：
  名称：

  2-苯基烷酸通过恶唑啉衍生物的不对称转化

  摘要：

  研究了 2-苯基链烷酸通过恶唑啉衍生物的不对称转化。(S)-苯丙氨醇在转化中用作手性助剂，得到的酸的光学产率为 29-53%。

  DOI：

  10.1246/cl.1981.217
• 作为产物：
  描述：

  L-苯丙氨醇 、 苯乙腈 在 cadmium(II) acetate 作用下， 以 氯苯 为溶剂， 反应 96.0h， 以84%的产率得到(4S)-(-)-2,4-dibenzyl-2-oxazoline
  参考文献：
  名称：

  Synthesis and structural characterization of enantiopure exo and endo six-membered oxazoline-derived palladacycles

  摘要：

  Direct palladation of (S)-4-beiizyl-2-methyl-2-oxazoline (1) and (S)-2-benzyl-4-tet-t-butyl-2-oxazoline (2) using Pd(OAC)(2) in MeCN afforded the corresponding mu-acetato-dimeric complexes with six-membered exo and endo palladacycles, respectively. The same complexes were obtained by reacting coordination complexes Pd(1)(2)(OAC)(2) and Pd(2)(2)(OAc)(2) with Pd(OAc)(2) in MeCN. Metalation of (S)-2,4-dibenzyl-2-oxazoline (3) with Pd(OAc)(2) in AcOH, MeCN or CH2CL2 resulted in the regiospecific formation of the six-membered endo palladacycle. The obtained mu-acetato-dimeric complexes were converted to the corresponding mu-chloro-dimeric derivatives 7, 11 and 13 by treatment with LiCl in acetone. The mononuclear PPh3 adducts 8, 12 and 14 were obtained by reacting dimers 7, 11 and 13 with PPh3 in benzene. NMR spectroscopy data supported the proposed structures of all complexes and suggested that exo and endo palladacycles in 8 and 12 have rigid boat conformations in CHCl3. The X-ray crystal structures of the mu-acetato dimer 6 with the exo palladacycle and the PPh3 adduct 14 with the endo metalacycle revealed boat conformation of both palladacycles and chiral twisted conformations delta(S) and lambda(S), respectively, of the oxazoline rings in the solid state. (c) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2007.10.011

文献信息

• Effect of Chain Length on Radical to Carbanion Cyclo-Coupling of Bromoaryl Alkyl-Linked Oxazolines:  1,3-Areneotropic Migration of Oxazolines
  作者：Laura J. Marshall、Mark D. Roydhouse、Alexandra M. Z. Slawin、John C. Walton

  DOI：10.1021/jo0620720

  日期：2007.2.1

  2-(1-phenyl-1,2,3,4-tetrahydronaphthalen-1-yl)-2-oxazoline, respectively. The major products from the precursor with a 5-C-atom spacer were derivatives of benzocycloheptane in which the oxazoline group had undergone a novel areneotropic migration from the end of the spacer to the benzo ring. The product from reaction of the corresponding 2-C-atom precursor was a 9-oxazolinophenanthrene derivative. EPR

  制备了具有2至6个C原子（n = 0-4）的烷基间隔基的2-卤苯基烷基-2-恶唑啉，其S RN考察了几种基本系统的1型反应。促进与相应的苯并环烷烃衍生物进行环偶联的最佳条件涉及在THF中使用LDA。具有3-C原子和4-C原子间隔基的前体可得到2-（1'-苯基茚满-1'-基）-2-恶唑啉和2-（1-苯基-1,2,3，分别为4-四氢萘-1-基）-2-恶唑啉。具有5-C原子间隔基的前体的主要产物是苯并环庚烷的衍生物，其中恶唑啉基团从间隔基的末端到苯并环经历了新的各向异性吸附。相应的2-C原子前体的反应产物是9-恶唑啉代菲衍生物。EPR光谱表明，LDA促进反应的中间体是产物苯并环烷烃的自由基阴离子。这支持一个SRN 1型链机制涉及通过间隔基团连接到氮杂酸酯离子的芳基的初始产生。分子内自由基与碳负离子的偶联随后产生了闭环的苯并环烷烃自由基阴离子，该阴离子将电子转移到更多的前体上。用含有手性2-恶唑啉
• Asymmetric Transformation of 2-Phenyl- and 2-Chloroalkanoic Acids<i>via</i>Chiral Oxazolines
  作者：Saizo Shibata、Hajime Matsushita、Hajime Kaneko、Masao Noguchi、Masahiko Saburi、Sadao Yoshikawa

  DOI：10.1246/bcsj.55.3546

  日期：1982.11

  Asymmetric transformation of racemic 2-phenyl- and 2-chloroalkanoic acids via oxazolines into the corresponding optically active acids was investigated using (S)-phenylalaninol as a chiral auxiliary. The asymmetric transformation was performed by metalation of the oxazolines with butyllithium followed by protonation of the resulting lithiooxazolines. 2-Phenyl- and 2-chloroalkanoic acids were obtained in the optical yields of 29–53% and 45–73%, respectively, by the acidic hydrolysis of the chiral oxazolines thus formed. The mechanism of the asymmetric transformation was discussed.

  以（S）-苯丙氨醇为手性助剂，研究了外消旋2-苯基-和2-氯烷酸通过恶唑啉转化为相应光学活性酸的不对称转化。通过用丁基锂对恶唑啉进行金属化，然后对生成的锂氧唑啉进行质子化，实现了不对称转化。通过手性恶唑啉的酸性水解，分别获得了光学收率29-53%和45-73%的2-苯基-和2-氯烷酸。讨论了不对称转化的机理。
• Solvent-free cyclopalladation on silica gel
  作者：Irina P. Smoliakova、Jessica L. Wood、Valeria A. Stepanova、Relindis Y. Mawo

  DOI：10.1016/j.jorganchem.2009.10.040

  日期：2010.2

  Tertiary, secondary and primary benzylamines, as well as structurally different oxazolines readily reacted with Pd(OAc)2 on silica gel to form cyclopalladated complexes containing a five or six-membered palladacycle with a (sp2)C–Pd or (sp3)C–Pd bond. The complexes were obtained in 45–98% yield, which is comparable with or exceeds the yields reported for preparation of the same compounds in solution

  叔，仲和伯苄胺，以及结构上不同的恶唑啉在硅胶上容易与Pd（OAc）2反应，形成包含五元或六元Palladacycle与（sp 2）C-Pd或（sp 3）的环钯配合物C–Pd键。获得的复合物的收率为45–98％，与报道的在溶液中制备相同化合物的收率相当或超过。脂族（sp 3）C–H键活化发生在SiO 2上的（S）-2-叔丁基-4-苯基-2-恶唑啉的环钯反应中 导致独家形成相应的内帕拉达环素，而据报道在AcOH中进行相同反应的有两种产物。
• Generation and hydrolysis of N-acyloxazolinium salts allowing regiospecific acylation of chiral amino alcohols
  作者：R. Alan Aitken、Alexandra M. Z. Slawin、Andrew Wilson

  DOI：10.1007/s10593-020-02707-3

  日期：2020.5

  N-benzoyloxazolinium salts gave the products of their ring hydrolysis: unsymmetrically diacylated amino alcohols whose structure was confirmed by X-ray diffraction in one case. Overall the method allows stepwise regiospecific N,O-diacylation of 2-amino alcohols.

  为了形成2-亚烷基-1，3-恶唑烷，手性2-恶唑啉已被N-烷基化和N-酰化。已经制备并表征了两种新的N-甲基恶唑啉鎓盐，但是碱处理导致它们分解。相反，尝试分离出三种N-苯甲酰恶唑啉鎓盐会产生其环水解的产物：一种是通过X射线衍射证实其结构的不对称二酰化氨基醇。总之，该方法允许2-氨基醇的逐步区域特异性的N，O-二酰化。
• SHIBATA, SAIZO;MATSUSHITA, HAJIME;KANEKO, HAJIME;NOGUCHI, MASAO;SABURI, M+, BULL. CHEM. SOC. JAP., 1982, 55, N 11, 3546-3551
  作者：SHIBATA, SAIZO、MATSUSHITA, HAJIME、KANEKO, HAJIME、NOGUCHI, MASAO、SABURI, M+

  DOI：——

  日期：——